The origin of light emission from newly discovered orange-red UV light emitting diodes, and their electronic properties are critical issues yet to be understood. In this study, X-ray absorption spectroscopy (XAS) and emission spectroscopy (XES) are utilized to examine the electronic structure of the Eu³⁺-doped Bi₂SrTa₂O₉ system. While no significant change in the electronic structure is observed around the Bi and Ta sites, variation around the Eu and Sr atoms is observed, along with even more significant changes in the O 2p states in the conduction band. Upon UV irradiation, Eu-induced states within the conduction band are observed and found to shift to the conduction band minimum upon substitution of Sr with Eu. This phenomenon is the result of the creation by Eu of an excitable state and the fact that Eu is more electronegative than Sr, such that the substitution lowers the Eu 4f5d–O 2p hybridized states. Consequently, the substitution reduces the energy of electron recombination between the valence and conduction bands, which is consistent with the red shift in the photoluminescence spectra. The presence of the newly formed hole states distributed over the O 2p states in the conduction band is strongly correlated with the emission intensity. The results and analyses demonstrate that Eu can be introduced to tailor the Eu–O hybridized states within the conduction band and change the route of recombination, suggesting that Eu is critically involved in light emission in these UV-induced orange-red emitting LED materials.